Methods for inserting silicon into phthalocyanines and naphthalocyanines

ABSTRACT

A simple, flexible, convenient method for making silicon phthalocyanines and naphthalocyanines by inserting silicon into metal-free phthalocyanines and metal-free naphthalocyanines is provided. The method comprises: providing a metal-free phthalocyanine or metal-free naphthalocyanine; reacting the metal-free phthalocyanine or metal-free naphthalocyanine with HSiCl 3  to provide a reaction product; then reacting the reaction product with water; and extracting a silicon phthalocyanine or a silicon naphthalocyanine. The invention also relates to novel phthalocyanines and naphthalocyanines. The phthalocyanines and naphthalocyanines are useful as photosensitizers and as dyes.

BACKGROUND OF THE INVENTION

In the past, silicon phthalocyanines generally have been made by the cyclization of a ring precursor. One such method involves reacting a diiminoisoindoline with a tetrachlorosilane. An example of this route is: ##STR1##

A disadvantage of this method is that it gives byproducts which are difficult to separate. The products are thus difficult to purify. Moreover certain phthalocyanine molecules are difficult, if not impossible, to assemble by this method.

SUMMARY OF THE INVENTION

The present invention provides a simple, flexible, convenient method for making silicon phthalocyanines and naphthalocyanines by inserting silicon into metal-free phthalocyanines and metal-free naphthalocyanines. The method comprises: providing a metal-free phthalocyanine or metal-free naphthalocyanine; reacting the metal-free phthalocyanine or metal-free naphthalocyanine with HSiCl₃ to provide a reaction product; then reacting the reaction product with water; and extracting a silicon phthalocyanine or a silicon naphthalocyanine. The invention also relates to novel phthalocyanines and naphthalocyanines.

The phthalocyanines and naphthalocyanines are useful as photosensitizers and as dyes.

DETAILED DESCRIPTION OF THE INVENTION

The present invention provides a simple, flexible, convenient method for making silicon phthalocyanines and silicon naphthalocyanines, hereinafter collectively referred to as "macrocycles", by inserting silicon into metal-free phthalocyanines and metal-free naphthalocyanines. The method is useful for making known compounds as well as novel compounds. The method comprises the following steps: first providing a metal-free phthalocyanine or a metal-free naphthalocyanine preferably having some substituent groups to make it soluble. The metal-free phthalocyanine or metal-free naphthalocyanine is then reacted with trichlorosilane, in a trichlorosilane to macrocycle ratio of from about 100:1 to about 1:1, preferably from about 30:1 to 10:1. The metal-free phthalocyanine or metal-free naphthalocyanine is preferably reacted with HSiCl₃ in the presence of an amine and an organic solvent. Preferably the amine is substituted with three alkyl groups, each alkyl group having from 1 to 10 carbon atoms; tri-n-propylamine is the preferred amine. The organic solvent employed in this step is inert and has a boiling point below 200° C. Suitable solvents include, for example, tetrahydrofuran, toluene, acetonitrile and CH₂ Cl₂ ; CH₂ Cl₂ is preferred. Benzene is less preferred. The reaction mixture is then hydrolyzed; and the hydrolysate is extracted with a volatile organic solvent. Preferably the volatile organic solvent has a boiling point below about 220° C. Preferred volatile solvents include, for example, toluene and CH₂ Cl₂.

The phthalocyanines are useful as photosensitizers, as discussed in U.S. Pat. No. 5,166,179 issued Nov. 24, 1992 and U.S. Pat. No. 5,484,778 issued Jan. 16 1996; which are specifically incorporated herein by reference. The phthalocyanines are also useful as dyes.

The phthalocyanines and naphthalocyanines when employed as photosensitizers preferably absorb light in the range of 700 to 950 nm, more preferably from 790 to 830 nm, most preferably from 800 to 810 nm. A further advantage of the novel phthalocyanine compounds is that they do not aggregate; aggregated phthalocyanine compounds have short excited state lifetimes and are not photoactive or are only weakly photoactive.

The present invention also relates to phthalocyanine compounds having the following general structure: ##STR2## wherein: R is Si(OH)₂, or Si(OSiR'₃)₂, where R' is an alkyl group having from 1-18 carbon atoms;

R¹ and R² are both H, or are joined to form a benzene ring;

R³ and R⁴ are both H, or are joined to form a benzene ring;

R⁵ and R⁶ are both H, or are joined to form a benzene ring;

R⁷ and R⁸ are both H, or are joined to form a benzene ring; and

R" is an alkyl group having from 1 to 18 carbon atoms.

Where R is Si(OSiR'₃)₂, R' is n--C₆ H₃₃, R" is n--C₄ H₉, and where: R1, R2, R3, R4, R5, R6, R7 and R8 are all H, the compound is SiN₀ P₄ (OBu)₈ (OSi (n--C₆ H₁₃) ₃)₂. Where R1 and R2 are joined to form a benzene ring, and R3, R4, R5, R6, R7 and R8 are all H, the compound is SiN₁ P₃ (OBu)₈ (OSi(n--C₆ H₁₃)₃)₂ ; where R1 and R2 are joined to form a benzene ring; R3 and R4 are joined to form a benzene ring, and R5, R6, R7 and R8 are all H, the compound is cis-SiN₂ P₂ (OBu)₈ (OSi(n--C₆ H₁₃)₃)₂ ; where R1 and R2 are joined to form a benzene ring; R5 and R6 are joined to form a benzene ring, and R3, R4, R7 and R8 are all H, the compound is trans-SiN₂ P₂ SiN₂ P₂ (OBu)8 (OSi (n--C₆ H₁₃)₃)₂ ; where R1 and R2 are joined to form a benzene ring; R3 and R4 are joined to form a benzene ring; R5 and R6 are joined to form a benzene ring; and R7 and R8 are both H, the compound is SiN₃ P₁ (OBu)₈ (OSi(n--C₆ H₁₃)₃)₂ ; where R1 and R2 are joined to form a benzene ring; R3 and R4 are joined to form a benzene ring; R5 and R6 are joined to form a benzene ring; and R7 and R8 joined to form a benzene ring, the compound is SiN₄ PO(OBu)₈ (OSi(n--C₆ H₁₃)₃)₂ also designated (SiNc (OBu)₈ (OSi (n--C₆ H₁₃)₃)₂.

Where R is Si(OH)₂, R" is n--C₄ H₉, R1, R2, R3, R4, R5, R6, R7 and R8 are all H, the compound is SiNOP₄ (OBu)₈ (OH)₂ ; where R1 and R2 are joined to form a benzene ring, and R3, R4, R5, R6, R7 and R8 are all H, the compound is SiN₁ P₃ (OBu)₈ (OH)₂ ; where R1 and R2 are joined to form a benzene ring, R3 and R4 are joined to form a benzene ring, and R5, R6, R7 and R8 are all H, the compound is cis-SiN₂ P₂ (OBu)₈ (OH)₂ ; where R1 and R2 are joined to form a benzene ring, R5 and R6 are joined to form a benzene ring, and R3, R4, R7 and R8 are all H, the compound is trans-SiN₂ P₂ (OBu)₈ (OH)₂ ; where R1 and R2 are joined to form a benzene ring, R3 and R4 are joined to form a benzene ring, R5 and R6 are joined to form a benzene ring, and R7 and R8 are both H, the compound is SiN₃ P₁ (OBu)₈ (OH)₂. Where R1 and R2 are joined to form a benzene ring; R3 and R4 are joined to form a benzene ring; R5 and R6 are joined to form a benzene ring; and R7 and R8 joined to form a benzene ring, the compound is SiN₄ P₀ (OBu)₈ (OH) 2 .

The present invention also relates to phthalocyanine compounds having the following general structure: ##STR3## wherein: two N, selected from the group of N1, N2, N3, and N4, have a H bound to or associated therewith;

and the structure contains from one to three benzene rings selected form the following:

a benzene ring formed by the joining of R¹ and R² ;

a benzene ring formed by the joining of R³ and R⁴ ;

a benzene ring formed by the joining of R⁵ and R⁶ ;

a benzene ring formed by the joining of R⁷ and R⁸ ; and

R" is an alkyl group having from 1 to 18 carbon atoms.

Where R" is n--C₄ H₉, R1 and R2 are joined to form a benzene ring, and R3, R4, R5, R6, R7 and R8 are all H, the compound is H₂ N₁ P₃ (OBu)₈ ; where R1 and R2 are joined to form a benzene ring, R3 and R4 are joined to form a benzene ring, and R5, R6, R7 and R8 are all H, the compound is cis-H₂ N₂ P₂ (OBu)₈ ; where R1 and R2 are joined to form a benzene ring, R5 and R6 are joined to form a benzene ring, and R3, R4, R7 and R8 are all H, the compound is trans-H₂ N₂ P₂ (OBu)₈ ; where R1 and R2 are joined to form a benzene ring, R3 and R4 are joined to form a benzene ring, R5 and R6 are joined to form a benzene ring, and R7 and R8 are both H, the compound is H₂ N₃ P₁ (OBu)₈.

Preparation of Silicon Phthalocyanines and Naphthalocyanines by Silicon Insertion

Silicon phthalocyanines and naphthalocyanines are made by insertion of a part of a silicon core precursor, HSiCl₃, into a metal-free phthalocyanine or a metal-free naphthalocyanine, for example: ##STR4## Since this example of the route entails the use of a reaction mixture containing tri-n-butylamine, it is believed that it involves the reaction of the ion-pairs HN(C₄ H,)₃ !⁺ HN_(4-x) P_(x) (OBu)₈ !⁻ Or HN(C₄ H₉)₃ !₂ ⁺ N_(4-x) P_(x) (OBu)₈ !²⁻ with the HSiCl₃ or a species derived from HSiCl₃.

The trialkylsiloxy compounds in which the R' alkyl group has 1 to 18 carbon atoms, are made by a route similar to that used for the tri-n-hexylsiloxy compounds as disclosed in example 8, except that instead of treating the dihydroxysilicon octaalkoxyphthalocyanine or the dihydroxysilicon octaalkoxynaphthalocyanine with (n--C₆ H₁₃)₃ SiCl, a trialkylhalosilane in which the alkyl groups have from 1 to 18 carbon atoms, is employed. Such trialkylhalosilane are made by conventional reactions such as the treatment of SiCl₄ with Grignard reagents as described in "Organosilicon Compounds", Eaborn, C., Acedemic Press, New York, (1960) pages 167-173. H₂ N_(4-x) P_(x) (OBu)₈

The route used for the preparation of the mixture containing H₂ N_(4-x) P_(x) (OBU)₈, Eq. 1, ##STR5## employs two nitriles instead of one. The individual compounds are readily separated by conventional techniques, such as, for example, column chromatography.

Compounds in which the R" groups contain an alkyl group having from 1-18 carbon atoms other than the butyl group are prepared by employing dialkoxydinitriles containing alkyl groups having 1 to 18 carbons other than the butyl group. Such dialkoxydinitriles containing alkyl groups having 1 to 18 carbons other than the butyl group, are made by the procedures described in "Octa-alkoxy Phthalocyanine and Naphthalocyanine Derivatives: Dyes with Q-Band Absorption in the Far Red or Near Infrared". Cook, M. J., et al., J. Chem. Soc. Perkin Trans 1 (1988)8 pages 2453-2458.

EXAMPLES

The following examples are intended to be illustrative and not limiting. The composition of the compounds was verified NMR spectroscopy supplemented in some cases by high-resolution fast-atom-bombardment mass spectroscopy.

Example 1 c-SiN₂ P₂ (OBu)₈ (OH)₂

A mixture of HSiCl₃ (0.70 mL, 7.0 mmol) and a solution of c--H₂ N₂ P₂ (OBu)₈ (52 mg, 0.040 mmol), tributylamine (2.0 mL, 8.4 mmol) and toluene (10 mL) was stirred at room temperature for 44 hours. The resultant was stirred with H₂ O (20 mL, 1.1 mol) for 30 minutes, and the hydrolysate obtained was stirred with triethylamine (10 mL, 99 mmol) for 30 minutes. The mixture formed was extracted with toluene 5 times, using about 40 mL each time, and the extracts were combined, filtered and evaporated to dryness with a rotary evaporator at 88° C. and about 5 torr. The solid was chromatographed (wet loading, toluene; Al₂ O₃ III, toluene, 1.5×20 cm; toluene-ethyl acetate; filtration: rotary evaporation at about 45° C. and about 20 torr), washed with pentane, and dried at 60° C. and about 25 torr. About 28.6 mg of the novel compound c-SiN₂ P₂ (OBu)₈ (OH)₂ was produced, for a yield of about 52%. UV-vis (λ_(max) (nm), toluyene), 805. NMR analysis revealed: ¹ H NMR (C₆ D₆): δ 9.19 (m, 1,27-Ar H; 4,24-Ar H), 7.66 (m, 2,26-Ar H; 3,25-Ar H), 7.55 (d, 10,18-Ar H). 7.40 (d, 11,17-Ar H), 5.41 (t, 28,32-OR-1 CH₂), 5.21 (t, 5,23-OR-1 CH₂), 4.94 (t, 9,19-OR-1 CH₂), 4.69 (t, 12,16-OR-1 CH₂), 2.29 (m, 5,23-OR-2 CH₂ ; 28,32-OR-2 CH₂), 2.21 (m, 9,19-OR-2 CH₂), 2.12 (m, 12,16-OR-2 CH₂), 1.83 (m, 28,32-OR-3 CH₂), 1.74 (m, 5,23-OR-3 CH₂), 1.57 (m, 9,19-OR-3 CH₂ ; 12,16-OR-3 CH₂), 1.13 (t, 28,32-OR-3 CH₂), 1.07 (t, 5,23-OR CH₃), 1.01 (t, 9,19-OR CH₃), 0.93 (t, 12,16-OR CH₃), -4.55 (s, br, OH). The compound, a dark-green solid, is soluble in toluene, CH₂ Cl₂ and pyridine, and slightly soluble in hexane.

Example 2 SiN₄ P₀ (OBu)₈ (OH)₂

SiN₄ P₀ (OBu)₈ (OH)₂ also designated SiNc(OBu)₈ (OH)₂, was prepared in a manner similar to that used for c-SiN₂ P₂ (OBu)₈ (OH)₂ except that H₂ N₄ P₀ (OBu)₈ was used instead of c-H₂ N₂ P₂ (OBu)₈. The yield was about 78%. UV-vis (λ_(max) nm), toluene),865. ¹ H NMR (C₆ D₆): δ 9.23 (m, 1,4,10,13,19,22,28,31-Ar H), 7.68 (m, 2,3,11,12,20,21,29,30-Ar H), 5.35 (t, OR-1 CH₂), 2.35 (m, OR-2 CH₂), 1.65 (m, OR-3 CH₂), 1.03 (t, OR CH₃), -3.79 (s, br, OH). ¹³ C NMR (C₆ D₆): δ 150.98 (6,8,15,17,24,26,33,35-Ar C), 148.37 (5,9,14,18,23,27,32,36-Ar C), 131.63 (4a,9a,13a,18a,22a,27a,31a,36a-Ar C), 127.73 (2,3,11,12,20,21,29,30-Ar C), 124.84 (1,4,10,13,19,22,28,31-Ar C), 122.71 (5a,8a,14a,17a,23a,26a,32a,35a-Ar C), 77.47 (OR-1 C), 33.40 (OR-2 C), 19.98 (OR-3 C), 14.48 (OR-4 C). The compound is a brown solid. It is soluble in toluene, CH₂ Cl₂ and pyridine, and slightly soluble in hexane. Its crystals are acicular.

Example 3 SiN₃ P₁ (OBu)₈ (OH)₂

SiN₃ P₁ (OBu)₈ (OH)₂ was prepared in a manner similar to that used for c-SiN₂ P₂ (OBu)₈ (OH)₂ except that H₂ N₃ P₁ (OBu)₈ was used. The yield of the novel compound SiN₃ P₁ (OBu)₈ (OH)₂ was about 56%. UV-vis (λ_(max) (nm), toluene), 825, 861. NMR analysis revealed the following: ¹ H NMR (C₆ D₆): δ 9.22 (m, 1,4-Ar H; 10,29-Ar H; 13,26-Ar H), 7.64 (m, 2,3-Ar H; 11,28-Ar H; 12,27-Ar H), 7.45 (s, 19,20-Ar H), 5.54 (t, 5,34-OR-1 CH₂), 5.36 (t, 9,30-OR-1 CH₂), 5.30 (t, 14,25-OR-1 CH₂), 4.75 (t, 18,21-OR-1 CH₂), 2.31 (m, 5,34-OR-2 CH₂ ; 9,30-OR-2 CH₂), 2.28 (m, 14,25-OR-2 CH₂ ; 18,21-OR-2 CH₂), 1.86 (m, 5,34-OR-3 CH₂ ; 9,30-OR-3 CH₂), 1.77 (m, 14,25-OR-3 CH₂ ; 18,21-OR-3 CH₂), 1.18 (t, 5,34-OR CH₃), 1.10 (m, 9,30-OR CH₃ ; 14,25-OR CH₃), 1.04(t, 18,21-OR CH₃). The compound, a brown solid, is soluble in toluene, CH₂ Cl₂ and pyridine, and slightly soluble in hexane.

Example 4 t-SiN₂ P₂ (OBu)₈ (OH)₂

t-SiN₂ P₂ (OBu)₈ (OH)₂, was prepared in a manner similar to that used for c-SiN₂ P₂ (OBu)₈ (OH)₂ except that t-H₂ N₂ P₂ (OBu)₈ was used. The yield was about 43%. UV-vis (λ_(max) (nm), toluene), 763, 859. NMR analysis revealed: ¹ H NMR (C₆ D₆): δ 9.24 (m, 9,12,25,28-Ar H), 7.69 (m, 10,11,26,27-Ar H), 7.44 (s, 2,3,18,19-Ar H), 5.39 (t, 8,13,24,29-OR-1 CH₂), 4.74 (t, 1,4,17,20-OR-1 CH₂), 2.31 (m, 8,13,24,29-OR-2 CH₂), 2.16 (m, 1,4,17,20-OR-2 CH₂), 1.82 (m, 8,13,24,29-OR-3 CH₂), 1.57 (m, 1,4,17,20-OR-3 CH₂), 1.13 (t, 8,13,24,29-OR CH₃), 0.95 (t, 1,4,17,20-OR CH₃). The compound, a brown solid, is soluble in toluene, CH₂ Cl₂ and pyridine, and slightly soluble in hexane.

Example 5 SiN P₃ (OBu)₈ (OH)₂

SiN₁ P₃ (OBu)₈ (OH)₂ was prepared in a manner similar to that used for c-SiN₂ P₂ (OBu)₈ (OH)₂ except that H₂ N₁ P₃ (OBu)₈ was used. The yield of novel SiN₁ P₃ (OBu)₈ (OH)₂ was about 69%. UV-vis (λ_(max) (nm), toluene), 762, 793. ¹ H NMR (C₆ D₆): δ 9.21 (m, 23,26-Ar H), 7.67 (m, 24,25-Ar H), 7.53 (d, 2,17-Ar H), 7.52 (s, 9,10-Ar H), 7.40 (d, 3,16-Ar H), 5.34 (t, 22,27-OR-1 CH₂), 4.91 (m, 1,18-OR-1 CH₂ ; 4,15-OR-1 CH₂), 4.67 (t, 8,11-OR-1 CH₂), 2.29 (m, 22,27-OR-2 CH₂), 2.20 (m, 1,18-OR-2 CH₂ ; 4,15-OR-2 CH₂ ; 8,11-OR-2 CH₂), 1.79 (m, 22,27-OR-3 CH₂), 1.72 (m, 1,18-OR-3 CH₂ ; 4,15-OR-3 CH₂ ; 8,11-OR-3 CH₂), 1.17 (t, 22,27-OR CH₃), 1.12 (t, 1,18-OR CH₃ ; 4,15-OR CH₃), 0.93 (t, 8,11-OR CH₃). The compound, a dark-green solid, is soluble in toluene, CH₂ Cl₂ and pyridine, and slightly soluble in hexane.

Example 6 SiNOP₄ (OBu)₈ (OH)₂

SiNOP₄ (OBu)₈ (OH)₂, also designated herein as SiPc(OBu)₈ (OH)₂, was prepared in a manner similar to that used for c-SiN₂ P₂ (OBu)₈ (OH)₂ except that H₂ N₀ P₄ (OBu)₈ was used. The yield was about 97%. UV-vis (λ_(max) (nm) toluene), 749. NMR analysis revealed: ¹ H NMR (C₆ D₆): δ 7.52 (s, Ar H), 4.87 (t, OR-1 CH₂) , 2.17 (m, OR-2 CH₂), 1.69 (m, OR-3 CH₂), 1.05 (t, OR CH₃). ¹³ C NMR (C₆ D₆): δ 152.89 (5,7,12,14,19,21,26,28-Ar C), 148.21 (1,4,8,11,15,18,22,25-Ar C), 127.47 (4a,7a,11a,14a,18a,21a,25a,28a-Ar C), 120.76 (2,3,9,10,16,17,23,24-Ar C), 73.26 (OR-1 C), 32.52 (OR-2 C), 19.94 (OR-3 C), 14.39 (OR-4 C). The SiNOP₄ (OBu)₈ (OH)₂, a green solid, is soluble in toluene, CH₂ Cl₂ and pyridine, and slightly soluble in hexane. The compound is not decomposed appreciably by treatment in succession with concentrated H₂ SO₄, H₂ O and NH₄ OH.

Example 7 SiN₀ P₄ (OBu)₈ (OH)₂

SiN₀ P₄ (OBu)₈ (OH)₂, also designated herein as SiPc(OBu)₈ (OH)₂ was made by an alternative synthesis to that of Example 6. A mixture of HSiCl₃ (0.1 mL, 1 mmol) and a solution of H₂ PC (OBu)₈ (50 mg, 0.046 mmol), N(n--C₃ H₇)₃ (1 mL, 5.2 mmol), CH₂ Cl₂ (15 mL) was stirred for 26 hours. The resultant was treated with 10 mL H₂ O and 5 mL N(C₂ H₇)₃, and the hydrolysate was extracted three times with CH₂ Cl₂ using 20 mL each time. The extracts were combined, filtered and evaporated to dryness with a rotary evaporator at 80° C. The solid was chromatographed (wet loading, CH₂ Cl₂ ; Al₂ O₃ III, CH₂ Cl₂, 1.5×20 cm; CH₂ Cl₂ -ethyl acetate-CH₃ OH; rotary evaporated at 30° C.) and dried at about 60° C. and about 25 torr. The compound weighed 45 mg, equivalent to 0.039 mmol, for a yield of 85%. The results of NMR analysis indicated that the compound was the same as that produced in example 6.

Example 8 c-SiN₂ P₂ (OBu)₈ (OSi(n--C₆ H₁₃)₃)₂.

A mixture containing 28 mg, that is, 0.020 mmol c-SiN₂ P₂ (OBu)₈ (OH)₂, (n--C₆ H₁₃)₃ SiCl (0.50 mL, 1.6 mmol), 2 mL pyridine and 20 mL toluene was refluxed for 2 hours and evaporated to dryness with a rotary evaporator at about 25° C. and 10 torr. The solid was chromatographed (wet loading, hexane; Al₂ O₃ III, hexane, 1.5×20 cm; hexane-toluene; filtration; rotary evaporation at 45° C. and about 20 torr). The solid was rechromatographed (toluene, about 0.1 g/mL; BioBeads S-X4 from Bio-Rad Labs, Richmond, Calif., 1.5×20 cm; toluene; rotary evaporation at 45° C. and about 20 torr), then dried at 60° C. and about 25 torr. The sample weight was 39.2 mg, for a yield of 96%. UV-vis (λ_(max) (nm), ε (M⁻¹ cm⁻¹)) (toluene, 2.0 μM) : 804, 1.9×10⁵. ¹ H NMR (C₆ D₆) δ 9.22 (m, 1,27-Ar H; 4,24-Ar H), 7.66 (m, 2,26-Ar H; 3,25-Ar H), 7.57 (d, 10,18-Ar H), 7.45 (d, 11,17-Ar H), 5.66 (t, 28,32-OR-1 CH₂), 5.52 (t, 5,23-OR-1 CH₂), 5.05 (t, 9,19-OR-1 CH₂), 4.83 (t, 12,16-OR-1 CH₂), 2.41 (m, 5,23-OR-2 CH₂ ; 28,32-OR-2 CH₂), 2.27 (m, 9,19-OR-2 CH₂ ; 12,16-OR-2 CH₂), 1.80 (m, 5,23-OR-3 CH₂ ; 28,32-OR-3 CH₂), 1.69 (m, 9,19-OR-3 CH₂ ; 12,16-OR-3 CH₂), 1.18 (t, 28,32-OR CH₃), 1.12 (t, 5,23-OR CH₃), 1.10 (t, 9,19-OR CH₃), 1.02 (t, 12,16-OR CH₃), 0.84 (m, SiR-5 CH₂), 0.62 (t, SiR CH₃), 0.46 (m, SiR-3 CH₂ ; SiR-4 CH₂), -0.47 (m, SiR-2 CH₂), -1.52 (m, SiR-1 CH₂). ¹³ C NMR (C₆ D₆): δ 152.70 (13,15-Ar C), 152.43 (8,20-Ar C), 151.75 (12,16-Ar C), 151.28 (9,19-Ar C), 151.19 (6,22-Ar C), 149.42 (29,31-Ar C), 147.43 (5,23-Ar C), 145.56 (28,32-Ar C), 132.19 (4a,23a-Ar C), 131.88 (27a,32a-Ar C), 127.75 (2,26-Ar C; 3,25-Ar C), 127.09 (12a,15a-Ar C), 126.15 (8a,19a-Ar C), 124.94 (1,27-Ar C), 124.86 (4,24-Ar C), 122.88 (5a,22a-Ar C), 122.15 (28a,31a-Ar C), 120.70 (10,18-Ar C), 118.19 (11,17-Ar C), 78.11 (28,32-OR-1 C), 77.85 (5,23-OR-1 C), 73.50 (9,19-OR-1 C), 72.58 (12,16-OR-1 C), 33.84 (28,32-OR-2 C; SiR-4 C), 33.49 (5,23-OR-2 C), 32.57 (9,19-OR-2 C), 32.43 (12,16-OR-2 C), 31.69 (SiR-3 C), 23.01 (SiR-5 C), 22.72 (SiR-2 C), 20.13 (5,23-OR-3 C; 28,32-OR-3 C), 20.04 (9,19-OR-3 C; 12,16-OR-3 C), 14.46 (5,23-OR-4 C; 9,19-OR-4 C; 12,16-OR-4 C; 28,32-OR-4 C; SiR CH₃), 14.26 (SiR-1 C). MS-HRFAB exact mass, m/z: calculated for C₁₀₈ H₁₆₂ N₈ O₁₀ Si₃ (M+H)⁺, 1816.1800; found, 1816.1767, 1816.1758. The compound, a dark-green solid, is very soluble in hexane, toluene, CH₂ Cl₂ and pyridine.

Example 9 SiN₄ P₀ (OBu)₈ (OSi (n--C₆ H₁₃)₃)₂

SiN₄ P₀ (OBu)₈ (OSi (n--C₆ H₁₃)₃)₂, also designated as SiNc (OBu)₈ (OSi (n--C₆ H₁₃)₃)₂, was prepared in a manner similar to that used for c-SiN₂ P₂ (OBu)₈ (OSi(n--C₆ H₁₃)₃)₂ except that SiN₄ P₀ (OBu)₈ (OH)₂ was used. The yield was about 94%. UV-vis (λ_(max) (nm), ε (M⁻¹ cm⁻¹)) (toluene, 1.2 μM): 864, 2.0×10⁵. ¹ H NMR (C₆ D₆): δ 9.23 (m, 1,4,10,13,19,22,28,31-Ar H), 7.67 (m, 2,3,11,12,20,21,29,30-Ar H), 5.55 (t, OR-1 CH₂), 2.46 (m, OR-2 CH₂), 1.77 (m, OR-3 CH₂), 1.10 (t, OR CH₃), 0.65 (m, SiR-5 CH₂), 0.39 (m, SiR-3 CH₂ ; SiR-4 CH₂ ; SiR CH₃), -0.34 (m, SiR-2 CH₂), -1.33 (m, SiR-1 CH₂). ¹³ C NMR (C₆ D₆): δ 151.01 (6,8,15,17,24,26,33,35-Ar C), 148.28 (5,9,14,18,23,27,32 36-Ar C), 131.73 (4a,9a,13a,18a,22a,27a,31a,36a-Ar C), 127.38 (2,3,11,12,20,21,29,30-Ar C), 124.83 (1,4,10,13,19,22,28,31-Ar C), 122.50 (5a,8a,14a,17a,23a,26a,32a,35a-Ar C), 77.73 (OR-1 C), 34.07 (SiR-4 C), 33.46 (OR-2 C), 31.77 (SiR-3 C), 22.93 (SiR-2 C; SiR-5 C), 20.11 (OR-3 C), 14.84 (SiR CH₃), 14.50 (OR-4 C), 13.99 (SiR-1 C). MS-HRFAB exact mass, m/z: calculated for C₁₁₆ H₁₆₆ N₈ O₁₀ Si₃ (M)⁺, 1915.2034; found, 1915.2068, 1915.2067. The compound is a brown solid. It is very soluble in hexane, toluene, CH₂ Cl₂ and pyridine. Its crystals are acicular.

Example 10 SiN₃ P₁ (OBu)₈ (OSi (n--C₆ H₁₃)₃)₂

SiN₃ P₁ (OBu)₈ (OSi(n--C₆ H₁₃)₃)₂ was prepared in a manner similar to that used for c-SiN₂ P₂ (OBu)₈ (OSi (n--C₆ H₁₃)₃)₂ except that SiN₃ P₁ (OBu)₈ (OH)₂ was used. The yield of the novel compound was about 89%. UV-vis (λ_(max) (nm) ε(M⁻¹ cm⁻¹)) (toluene, 2.2 μM): 820, 1.6×10⁵ ; 857, 1.3×10⁵. ¹ H NMR (C₆ D₆): δ 9.24 (m, 1,4-Ar H; 10,29-Ar H; 13,26-Ar H), 7.67 (m, 2,3-Ar H; 11,28-Ar H; 12,27-Ar H), 7.48 (s, 19,20-Ar H), 5.66 (t, 5,34-OR-1 CH₂), 5.57 (t, 9,30-OR-1 CH₂), 5.15 (t, 14,25-OR-1 CH₂), 4.88 (t, 18,21-OR-1 CH₂), 2.44 (m, 5,34-OR-2 CH₂ ; 9,30-OR-2 CH₂), 2.33 (m, 14,25-OR-2 CH₂ ; 18,21-OR-2 CH₂), 1.87 (m, 5,34-OR-3 CH₂ ; 9,30-OR-3 CH₂), 1.76 (m, 14,25-OR-3 CH₂ ; 18,21-OR-3 CH₂), 1.18 (t, 5,34-OR CH₃), 1.10 (m, 9,30-OR CH₃ ; 14,25-OR CH₃), 1.05 (t, 18,21-OR CH₃), 0.75 (m, SiR-5 CH₂), 0.51 (t, SiR CH₃), 0.42 (m, SiR-3 CH₂ ; SiR-4 CH₂), -0.39 (m, SiR-2 CH₂), -1.41 (m, SiR-1 CH₂). ¹³ C NMR (C₆ D₆): δ 152.43 (17,22-Ar C), 151.45 (15,24-Ar C), 151.29 (8,31-Ar C), 150.87 (6,33-Ar C), 150.02 (18,21-Ar C), 149.64 (14,25-Ar C), 147.80 (9,30-Ar C), 146.02 (5,34-Ar C), 132.06(4a,34a-Ar C), 131.91 (9a,29a-Ar C), 131.56(13a,25a-Ar C), 127.53 (2,3-Ar C), 127.40 (11,28-Ar C; 12,27-Ar C), 126.13 (17a,21a-Ar C), 124.89 (1,4-Ar C; 10,29-Ar C), 124.78 (13,26-Ar C), 122.86 (5a,33a-Ar C), 122.51 (8a,30a-Ar C), 122.23 (14a,24a-Ar C), 118.68 (19,20-Ar C), 77.95 (5,34-OR-1 C), 77.85 (9,30-OR-1 C), 77.76 (14,25-OR-1 C), 72.75 (18,21-OR-1 C), 33.97 (SiR-4 C), 33.73 (5,34-OR-2 C), 33.50 (9,30-OR-2 C), 33.45 (14,25-OR-2 C), 32.45 (18,21-OR-2 C), 31.74 (SiR-3 C), 22.98 (SiR-5 C), 22.84 (SiR-2 C), 20.11 (5,34-OR-3 C; 9,30-OR-3 C; 14,25-OR-3 C; 18,21-OR-3 C), 14.66 (SiR-CH₃), 14.50 (5,34-OR-4 C; 9,30-OR-4 C; 14,25-OR-4 C; 18,21-OR-4 C), 14.14 (SiR-1 C). MS-HRFAB exact mass, m/z: calcd for C₁₁₂ H₁₆₄ N₈ O₁₀ Si₃ (M)⁺, 1865.1878; found, 1865.1915, 1865.1974. The compound, a brown solid, is very soluble in toluene, hexane, CH₂ Cl₂ and pyridine.

Example 11 t-SiN₂ P₂ (OBU)₈ (OSi (n--C₆ H₁₃)₃)₂

t-SiN₂ P₂ (OBu)₈ (OSi (n--C₆ H₁₃)₃)₂ was prepared in a manner similar to that used for c-SiN₂ P₂ (OBu)₈ (OSi (n--C₆ H₁₃)₃)₂ except that t-SiN₂ P₂ (OBU)₈ (OH)₂ was used. The yield was about 79a. UV-vis (λ_(max) (nm) ε (M⁻¹ cm⁻¹)) (toluene, 1.5 μM): 760, 1.5×10⁵ ; 851, 1.2×10⁵. ¹ H NMR (C₆ D₆) : δ 9.24 (m, 9,12,25,28-Ar H), 7.68 (m, 10,11,26,27-Ar H), 7.50 (s, 2,3,18,19-Ar H), 5.62 (t, 8,13,24,29-OR-1 CH₂), 4.89 (t, 1,4,17,20-OR-1 CH₂), 2.38 (m, 8,13,24,29-OR-2 CH₂), 2.32 (m, 1,4,17,20-OR-2 CH₂), 1.84 (m, 8,13,24,29-OR-3 CH₂), 1.70 (m, 1,4,17,20-OR-3 CH₂), 1.18 (t, 8,13,24,29-OR CH₃), 1.04 (t, 1,4,17,20-OR CH₃), 0.85 (m, SiR-5 CH₂), 0.62 (t, SiR CH₃), 0.45 (m, SiR-3 CH₂ ; SiR-4 CH₂), -0.49 (m, SiR-2 CH₂), -1.56 (m, SiR-1 CH₂). ¹³ C NMR (C₆ D₆): δ 152.67 (5,16,21,32-Ar C), 151.12 (1,4,7,20-Ar C), 149.02 (7,14,23,30-Ar C; 8,13,24,29-Ar C), 131.37 (8a,12a,24a,28a-Ar C), 127.75 (10,11,26,27-Ar C), 126.95 (4a,16a,20a,32a-Ar C), 126.41 (7a,13a,23a,29a-Ar C), 124.82 (9,12,25,28-Ar C), 119.52 (2,3,18,19-Ar C), 78.00 (8,13,24,29-OR-1 C), 72.86 (1,4,17,20-OR-1 C), 33.81 (SiR-4 C), 33.73 (8,13,24,29-OR-2 C), 32.47 (1,4,17,20-OR-2 C), 31.68 (SiR-3 C), 23.00 (SiR-5 C), 22.69 (SiR-2 C), 20.10 (1,4,17,20-OR-3 C; 8,13,24,29-OR-3 C), 14.49 (1,4,17,20-OR-4 C; 8,13,24,29-OR-4 C), 14.41 (SiR CH₃), 14.26 (SiR-1 C). MS-HRFAB exact mass, m/z: calculated for C₁₀₈ H₁₆₂ N₈ O₁₀ Si₃ (M+H)⁺, 1816.1800; found, 1816.1742, 1816.1775. The compound is a brown solid. It is very soluble in hexane, toluene, CH₂ Cl₂, and pyridine.

Example 12 SiN₁ P₃ (OBu)₈ (OSi (n--CH₁₃)₃)₂

SiN₁ P₃ (OBu)₈ OSi(n--C₆ H₁₃)₃)₂ was prepared in a manner similar to that used for c-SiN₂ P₂ (OBu)₈ (OSi (n--C₆ H₁₃)₃)₂ except that SiN₁ P₃ (OBu)₈ (OH)₂ was used. The yield of this novel compound was about 69%. UV-vis (λ_(max) (nm), ε (M⁻¹ cm⁻¹)) (toluene, 2.1 μM) : 761, 2.2×10⁵ ; 794, 1.5×10⁵. ¹ H NMR (C₆ D₆): δ 9.22 (m 23,26-Ar H), 7.67 (m, 24,25-Ar H), 7.58 (d, 2,17-Ar H), 7.55 (s, 9,10-Ar H), 7.45 (d, 3,16-Ar H), 5.62 (t, 22,27-OR-1 CH₂), 5.06 (t, 1,18-OR-1 CH₂), 5.01 (t, 4,15-OR-1 CH₂), 4.83 (t, 8,11-OR-1 CH₂), 2.36 (m, 22,27-OR-2 CH₂), 2.28 (m, 1,18-OR-2 CH₂ ; 4,15-OR-2 CH₂ ; 8,11-OR-2 CH₂), 1.78 (m, 22,27-OR-3 CH₂), 1.68 (m, 1,18-OR-3 CH₂ ; 4,15-OR-3 CH₂ ; 8,11-OR-3 CH₂), 1.17 (t, 22,27-OR CH₃), 1.12 (m, 1,18-OR CH₃ ; 4,15-OR CH₃), 1.02 (t, 8,11-OR CH₃), 0.92 (m,SiR-5 CH₂), 0.72 (t, SiR CH₃), 0.55 (m, SiR-4 CH₂), 0.42 (m, SiR-3 CH₂), -0.58 (m, SiR-2 CH₂), -1.67 (m, SiR-1 CH₂). ¹³ C NMR (C₆ D₆): δ 152.95 (7,12-Ar C), 152.74 (5,14-Ar C; 19,30-Ar C), 152.69 (21,28-Ar C), 151.63 (1,18-Ar C; 4,15-Ar C; 8,11-Ar C), 150.20 (22,27-Ar C), 131.99 (22a,26a-Ar C), 127.35 (24,25-Ar C), 127.11 (7a,11a-Ar C), 126.94 (21a,27a-Ar C), 126.43 (4a,14a-Ar C; 18a,30a-Ar C), 124.89 (23,26-Ar C), 121.57 (2,17-Ar C), 120.17 (3,16-Ar C), 118.96 (9,10-Ar C), 78.15 (22,27-OR-1 C), 73.67 (1,18-OR-1 C; 4,15-OR-1 C), 72.65 (8,11-OR-1 C), 33.70 (22,27-OR-2 C; SiR-4 C), 32.61 (1,18-OR-2 C), 32.54 (4,15-OR-2 C), 32.44 (8,11-OR-2 C), 31.64 (SiR-3 C), 23.04 (SiR-5 C), 22.56 (SiR-2 C), 20.12 (1,18-OR-3 C; 22.27-OR-3 C), 20.03 (4,15-OR-3 C; 8,11-OR-3 C), 14.39 (1,18-OR-4 C; 4,15-OR-4 C; 8,11-OR-4 C; 22,27-OR-4 C; SiR CH₃), 14.20 (SiR-i C). MS-HRFAB exact mass, m/z: calcd for C₁₀₄ H₁₆₀ N₈ O₁₀ Si₃ (M)⁺, 1765.1565; found, 1765.1583, 1765.1527. The compound is a dark-green solid. It is very soluble in hexane, toluene, CH₂ Cl₂ and pyridine.

Example 13 SiNOP₄ (OBu)₈ (OSi(n--C₆ H₁₃)₃)₂

SiNOP₄ (OBu)₈ (OSi(n--C₆ H₁₃)₃)₂ also designated as (SiPc(OBu)₈ (Osi(n--C₆ H₁₃)₃)₂, was prepared in a manner similar to that used for c-SiN₂ P₂ (OBu)₈ (OSi (n--C₆ H₁₃)₃)₂ except that SiN₀ P₄ (OBu)₈ (OH)₂ was used. The yield was about 88%. UV-vis (λ_(max) (nm) ε (M⁻¹ cm⁻¹)) (toluene, 1.7 μM): 747, 2.3×10⁵. ¹ H NMR (C₆ D₆): δ 7.57 (s, Ar H) , 5.03 (t, OR-1 CH₂), 2.27 (m, OR-2 CH₂) 1.77 (m, OR-3 CH₂), 1.11 (t, OR CH₃), 0.99 (m, SiR-5 CH₂), 0.82 (t, SiR CH₃), 0.59 (m, SiR-4 CH₂), 0.39 (m, SiR-3 CH₂), -0.70 (m SiR-2 CH₂), -1.83 (m, SiR-1 CH₂). ¹³ C NMR (C₆ D₆): δ 153.02 (5,7,12,14,19,21,26,28-Ar C), 148.16 (1,4,8,11,15,18,22,25-Ar C), 127.38 (4a,7a,11a,14a,18a,21a,25a,28a-Ar C), 121.07 (2,3,9,10,16,17,23,24-Ar C), 73.53 (OR-1 C), 33.58 (SiR-4 C), 32.58 (OR-2 C), 31.58 (SiR-3 C), 23.07 (SiR-5 C), 22.40 (SiR-2 C), 20.02 (OR-3 C), 14.50 (SiR CH₃), 14.43 (OR-4 C), 13.91 (SiR-1 C). MS-HRFAB exact mass, m/z: calcd for C₁₀₀ H₁₅₈ N₈ O₁₀ Si₃ (M)⁺, 1715.1408; found, 1715.1384, 1715.1453

The compound, a green solid, is very soluble in hexane, toluene, CH₂ Cl₂ and pyridine.

Example 14 SiPc(dib),₄ (OBu)₈ (OH)₂

SiPc(dib)₄ (OBu)₈ (OH)₂ has a structure similar to SiN₄ P₀ (OBu)₈ (OH)₂, except that R1 and R2 are joined to form a triptycene ring; R3 and R4 are joined to form a triptycene ring; R5 and R6 are joined to form a triptycene ring; and R7 and R8 joined to form a triptycene ring, rather than benzene rings. The starting material, H₂ Pc(dib)₄ (OBu)₈ is made according to the process disclosed in Rihter, B. D., et al., "Two New Sterically Hindered Phthalocyanines: Synthetic and Photodynamic Aspects", Photochemistry and Photobiology (1992) Volume 55, pages 677-680.

Under Ar, a mixture of HSiCl₃ (0.15 mL, 1.6 mmol) and a solution of H₂ Pc(dib)₄ (OBu)₈ (103 mg, 0.0574 mmol), N(n--C₃ H₇)₃ (5 mL, 26 mmol), CH₃ CN (20 mL), and tetrahydrofuran (20 mL) that had been dried by distilling off about 5 mL of distillate was stirred at room temperature for 10 minutes, refluxed for 3 hours, and stirred at room temperature for 60 hours. The resulting slurry was treated with 30 mL H₂ O and 20 mL N(C₂ H₅)₃, and extracted with CH₂ Cl₂ (3 times, 50 mL each time). The extracts were combined, filtered and evaporated to dryness by rotary evaporation at 80° C. and about 20 torr. The solid was chromatographed (wet loading, toluene; Al₂ O₃ III, toluene, 1.5×20 cm; toluene-ethyl acetate; filtration; rotary evaporation at 45° C. and about 20 torr). The solid was rechromatographed (toluene, about 0.1 g/mL; Biobeads S-X4, 1.5×20 cm; toluene; rotary evaporation at 45° C. and about 20 torr), and dried at about 60° C. and 25 torr. About 48 mg, that is, 0.026 mmol, of the novel compound was produced, providing a yield of about 45%.

UV-vis (λ_(max) (nm), ε (M⁻¹ cm⁻¹)) (toluene, 1.8 μM): 745, 2.7×10⁵. ¹ H NMR(C₆ D₆): δ 7.64 (m, 1,4,12,15,23,26,34,37,51,54,57,60,63,66, 69,72-Ar H), 7.01 (m,2,3,13,14,24,25,35,36,52,53,58,59,64,65,70, 71-Ar H), 6.75 (s,5,11,16,22,27,33,38,44-CH), 5.06 (t, OR-1 CH₂), 2.34 (m, OR-2 CH₂), 1.63 (m, OR-3 CH₂), 1.18 (t, OR CH₃), -5.40(s, br, OH). MS-HRFAB exact mass, m/z: calculated for C₁₂₀ H₁₁₄ N₈ O₁₀ Si (M)⁺, 1854.8427; found, 1854.8504, 1854.8451.

Example 15 SiPc(OEt)₈ (OH)₂

A mixture of HSiCl₃ (0.2 mL, 2 mmol) and a solution of H₂ Pc(OEt) B (106 mg, 0.12 mmol), N(n--C₃ H₇)₃ (4 mL, 21 mmol), CH₂ Cl₂ (40 mL) was stirred for 48 hours. The resultant was treated with H₂ O (20 mL) and N(C₂ H₅)₃ (10 mL), and the hydrolysate was extracted with CH₂ Cl₂ 3 times, using 20 mL each time. The extracts were combined, filtered and evaporated to dryness with a rotary evaporator at 80° C. The solid was chromatographed (wet loading, CH₂ Cl₂ ; Al₂ O₃ III, CH₂ Cl₂, 1.5×20 cm; CH₂ Cl₂ -ethyl acetate; rotary evaporation at 30° C., and dried at about 60° C. and 25 torr. The compound weighed 98 mg, equivalent to 0.10 mmol and thus the yield was 88%. UV-vis (λ_(max) nm) toluene): 747. ¹ H NMR (C₆ D₆): δ 7.45 (s, Ar H), 4.81 (t, OR CH₂), 1.65 (t, OR CH₃). The compound is a green solid, is soluble in CH₂ Cl₂ and slightly soluble in toluene. The results of NMR analysis showed that the desired compound had been made.

Example 16 H₂ N₄ P₀ (OBu)₈

H₂ N₄ P₀ (OBu)₈ also designated H₂ Nc(OBu)₈, was prepared as follows. Under Ar, a mixture of 3,6-dibutoxy-1,2-benzenedicarbonitrile (279 mg, 1.00 mmol), 1,4-dibutoxy-2,3-naphthalenedicarbonitrile (326 mg, 1.00 mmol) and 1-butanol (22 mL) was brought to reflux, treated with Li shot (pentane washed, 450 mg, 65.0 mmol), refluxed for 1 hour and cooled. The resulting solution was stirred with H₂ O (25 mL, 1.4 mol) for 2.5 hours, and the hydrolysate obtained was extracted with toluene by stirring it with 50 mL toluene five times. The extracts were combined, filtered and evaporated to dryness with a rotary evaporator at 60° C. and about 30 torr, and the solid was extracted with 50 mL of toluene. The extract was evaporated to dryness with a rotary evaporator at 60° C. and about 30 torr. About 600 mg of the product, which is designated H₂ N_(4-x) P_(x) (OBu)₈ , and which is a mixture of H₂ N₄ P₀ (OBU)₈, H₂ N₃ P₁ (OBu)₈, c--H₂ N₂ P₂ (OBu)₈, t-H₂ N₂ P₂ (OBu)₈, H₂ N₁ P₃ (OBu)₈, and H₂ N₀ P₄ (OBu)₈, was produced. H₂ N_(4-x) P_(x) (OBu)₈, a greenish-brown solid, is soluble in toluene, CH₂ Cl₂ and pyridine, and slightly soluble in hexane. H₂ N₄ P₀ (OBu)₈ also designated "H₂ Nc(OBu)₈ " was isolated from the H₂ N₄ XPX(OBu)₈ mixture by subjecting 600 mg of the H₂ N_(4-x) P_(x) (OBU)₈ to column chromatography (wet loading, hexane; Al₂ O₃ III, hexane, 1.5×20 cm; hexane; filtration; rotary evaporation at 45° C. and about 20 torr). The solid isolated was washed with 5 mL pentane, dried at about 60° C and about 25 torr. The H₂ N₄ P₀ (OBu)₈ weighed 5 mg, which represented a yield of 1% of weight of H₂ N_(4-x) P_(x) (OBu)₈. UV-vis (λ_(max) (nm), ε (M⁻¹ cm⁻¹)) (toluene, 2.1 μM): 862, 2.0×10⁵. NMR analysis revealed: ¹ H NMR (C₆ D₆): δ 9.23 (m, 1,4,10,13,19,22,28,31-Ar H), 7.68 (m, 2,3,11,12,20,21,29,30-Ar H), 5.40 (t, OR-1 CH₂), 2.38 (m, OR-2 CH₂), 2.27 (s, NH), 1.67 (m, OR-3 CH₂), 1.03 (t, OR CH₃). ¹³ C NMR (C₆ D₆): δ 150.59 (5,9,14,18,23,27,32,36-Ar C; 6,8,15,17,24,26,33,35-Ar C), 131.54 (4a,9a,13a,18a,22a,27a,31a,36a-Ar C), 127.60 (2,3,11,12,20,21,29,30-Ar C), 124.91 (1,4,10,13,19,22,28,31-Ar C), 123.51 (5a,8a,14a,17a,23a,26a,32a,35a-Ar C), 77.24 (OR-1 C), 33.34 (OR-2 C), 20.07 (OR-3 C), 14.49 (OR-4 C). The H₂ N₄ P₀ (OBu)₈, a brown solid, is soluble in toluene, CH₂ Cl₂, pyridine and slightly soluble in hexane.

Example 17 H₂ N₃ P₁ (OBu)₈

H₂ N₃ P₁ (OBu)₈ was isolated from the H₂ N_(4-x) P_(x) (OBu)₈ mixture of example 16 by continuing the chromatography with toluene. The fraction isolated yielded 34 mg of the novel compound H₂ N₃ P₁ (OBu)₈, which represents 6% of weight of H₂ N_(4-x) P_(x) (OBu)₈. UV-vis (λ_(max) nm) ε (M⁻¹ cm⁻¹)) (toluene, 1.9 μM) 814, 0.99×10⁵ ; 851, 0.89×10⁵. ¹ H NMR (C₆ D₆) δ 9.23 (m, 1,4-Ar H; 10,29-Ar H; 13,26-Ar H), 7.69 (m, 2,3-Ar H; 11,28-Ar H; 12,27-Ar H), 7.44 (s, 19,20-Ar H), 5.55 (t, 5,34-OR-1 CH₂), 5.39 (t, 9,30-OR-1 CH₂), 5.31 (t, 14,25-OR-1 CH₂), 4.75 (t, 18,21-OR-1 CH₂), 2.34 (m, 5,34-OR-2 CH₂ ; 9,30-OR-2 CH₂), 2.24 (m, 14,25-OR-2 CH₂ ; 18,21-OR-2 CH₂), 1.91 (s, NH), 1.85 (m, 5,34-OR-3 CH₂ ; 9,30-OR-3 CH₂), 1.66 (m, 14,25-OR-3 CH₂ ; 18,21-OR-3 CH₂) , 1.13 (t, 5,34-OR CH₃) , 1.02 (m, 9,30-OR CH₃ ; 14,25-OR CH₃), 0.96 (t, 18,21-OR CH₃). ¹³ C NMR (C₆ D₆) δ 152.22 (17,22-Ar C), 151.50 (18,21-Ar C), 150.63 (5,34-Ar C; 6,33-Ar C), 149.99 (8,31-Ar C; 9,30-Ar C; 14,25-Ar C; 15,24-Ar C), 131.97 (4a,34a-Ar C), 131.67 (9a,29a-Ar C; 13a,25a-Ar C), 127.73 (17a,21a-Ar C), 127.53 (2,3-Ar C), 127.41 (11,28-Ar C; 12,27-Ar C), 125.69 (1,4-Ar C), 124.91 (10,29-Ar C; 13,26-Ar C), 121.42(5a,33a-Ar C; 8a,30a-Ar C; 14a,24a-Ar C), 117.28 (19,20-Ar C), 77.35 (5,34-OR-1 C; 9,30-OR-1 C), 77.27 (14,25-OR-1 C), 72.23 (18,21-OR-1 C), 33.67 (5,34-OR-2 C), 33.31 (9,30-OR-2 C; 14,25-OR-2 C), 32.37 (18,21-OR-2 C), 20.33 (5,34-OR-3 C), 20.12 (9,30-OR-3 C; 14,25-OR-3 C), 20.03 (18,21-OR-3 C), 14.46 (5,34-OR-4 C; 9,30-OR-4 C; 14,25-OR-4 C; 18,21-OR-4 C). MS-HRFAB exact mass, m/z: calculated for C₇₆ H₈₈ N₈ O₈ (M+H)⁺, 1241.6803; the mass found was 1241.6807, 1241.6795. The H₂ N₃ P₁ (OBu)₈, a brown solid, is soluble in toluene, CH₂ Cl₂, pyridine and slightly soluble in hexane.

Example 18 c-H₂ N₂ P₂ (OBu)₈

c-H₂ N₂ P₂ (OBu)₈ was isolated from the H₂ N₂ P₂ (OBu)₈ mixture of Example 16 by continuing the chromatography with a 1:1 mixture of toluene and CH₂ Cl₂. The fraction separated yielded 62 mg of the novel compound c-H₂ N₂ P₂ (OBu)₈, which represents 10% of weight of H₂ N_(4-x) P_(x) (OBu)₈. UV-vis (λ_(max) (nm), ε (M⁻¹ cm⁻¹)) (toluene, 2.2 μM): 807, 1.9×10⁵. ¹ H NMR (C₆ D₆): δ 9.21 (m, 1,27-Ar H; 4,24-Ar H) , 7.67 (m, 2,26-Ar H; 3,25-Ar H), 7.52 (d, 10,18-Ar H), 7.40 (d, 11,17-Ar H), 5.51 (t, 28,32-OR-1 CH₂), 5.30 (t, 5,23-OR-1 CH₂), 4.95 (t, 9,19-OR-1 CH₂), 4.71 (t, 12,16-OR-1 CH₂), 2.31 (m, 5,23-OR-2 CH₂ ; 28,32-OR-2 CH₂), 2.20 (m, 9,19-OR-2 CH₂ ; 12,16-OR-2 CH₂), 1.80 (m, 5,23-OR-3 CH₂ ; 28,32-OR-3 CH₂), 1.62 (m, 9,19-OR-3 CH₂ ; 12,16-OR-3 CH₂), 1.54 (s, NH), 1.10 (t, 28,32-OR CH₃), 1.06 (t, 5,23-OR CH₃), 1.00 (t, 9,19-OR CH₃), 0.94 (t, 12,16-OR CH₃). ¹³ C NMR (C₆ D₆): δ 152.38 (13,15-Ar C), 152.20 (8,20-Ar C; 9,19-Ar C; 12,16-Ar C), 150.70 (6,22-Ar C; 29,31-Ar C), 150.33 (5,23-Ar C; 28,32-Ar C) 131.98 (27a,32a-Ar C), 131.21 (4a,23a-Ar C), 126.85 (8a,19a-Ar C; 12a,15a-Ar C), 127.75 (2,26-Ar C; 3,25-Ar C), 125.01 (1,27-Ar C), 124.92 (4,24-Ar C), 123.71 (5a,22a-Ar C), 123.11 (28a,31a-Ar C). 119.89 (10,18-Ar C), 117.59 (11,17-Ar C), 77.50 (28,32-OR-1 C), 77.29 (5,23-OR-1 C), 72.98 (9,19-OR-1 C), 72.16 (12,16-OR-1 C), 33.61 (28,32-OR-2 C), 33.29 (5,23-OR-2 C), 32.53 (9,19-OR-2 C), 32.38 (12,16-OR-2 C), 20.09 (5,23-OR-3 C; 28,32-OR-3 C), 20.01 (9,19-OR-3 C; 12,16-OR-3 C), 14.44 (5,23-OR-4 C; 9,19-OR-4 C; 12,16-OR-4 C; 28,32-OR-4 C). MS-HRFAB exact mass, m/z calculated for C₇₂ H₈₆ N₈ O₈ (M+H)⁺, is 1191.6647; the mass found, was 1191.6677, 1191.6598.

The c-H₂ N₂ P₂ (OBu)₈, a dark-green solid, is soluble in toluene, CH₂ Cl₂ pyridine and slightly soluble in hexane.

Example 19 t-H₂ N₂ P₂ (OBu)₈

t-H₂ N₂ P₂ (OBu)₈ was isolated from the H₂ N_(4-x) P_(x) (OBu)₈ mixture of Example 16 by continuing the chromatography with CH₂ Cl₂. The resulting fraction yielded 12 mg of t-H₂ N₂ P₂ (OBu)₈ which represents 2% of weight of H₂ N_(4-x) P_(x) (OBu)₈. UV-vis (λ_(max) (nm) ε (M⁻¹ cm⁻¹)) (toluene, 1.7 μM) : 750, 0.98×10⁵ ; 852, 0.75×10⁵. ¹ H NMR (C₆ D₆): δ 9.23 (m, 9,12,25,28-Ar H), 7.69 (m, 10,11,26,27-Ar H), 7.47 (s, 2,3,18,19-Ar H), 5.48 (t, 8,13,24,29-OR-1 CH₂), 4.75 (t, 1,4,17,20-OR-1 CH₂), 2.32 (m, 8,13,24,29-OR-2 CH₂), 2.22 (m, 1,4,17,20-OR-2 CH₂), 1.83 (m, 8,13,24,29-OR-3 CH₂), 1.60 (m, 1,4,17,20-OR-3 CH₂), 1.11 (t, 8,13,24,29-OR CH₃), 0.95 (t, 1,4,17,20-OR CH₃). ¹³ C NMR (C₆ D₆): δ 152.20 (1,4,17,20-Ar C; 5,16,20,32-Ar C), 150.72 (7,14,23,30-Ar C; 8,13,24,29-Ar C), 131.89(8a,12a,24a,28a-Ar C), 127.36 (10,11,26,27-Ar C), 127.17 (4a,16a,20a,32a-Ar C), 126.15 (7a,13a,23a,29a-Ar C), 125.02 (9,12,25,28-Ar C), 118.32 (2,3,18,19-Ar C), 77.42 (8,13,24,29-OR-1 C), 72.37 (1,4,17,20-OR-1 C), 33.65 (8,13,24,29-OR-2 C), 32.35 (1,4,17,20-OR-2 C), 20.10 (1,4,17,20-OR-3 C; 8,13,24,29-OR-3 C), 14.46 (1,4,17,20-OR-4 C; 8,13,24,29-OR-4 C). MS-HRFAB exact mass, m/z: calculated for C₇₂ H₈₆ N₈ O₈ (M+H)⁺, 1191.6647; the mass found, was 1191.6632, 1191.6592. The t-H₂ N₂ P₂ (OBu)₈ , a brown solid, is soluble in toluene, CH₂ Cl₂, pyridine and slightly soluble in hexane.

Example 20 H₂ N₁ P₃ (OBu)₈

H₂ N₁ P₃ (OBu)₈ was isolated from the H₂ N_(4-x) P_(x) (OBu)₈ mixture of Example 16 by continuing the chromatography with a 1:1 mixture of toluene and ethyl acetate. The fraction isolated yielded 102 mg of the novel compound H₂ N₁ P₃ (OBu)₈, which represents 17% of weight of H₂ N_(4-x) P_(x) (OBu)₈. UV-vis (λ_(max) nm), ε (M⁻¹ cm⁻¹)) (toluene, 1.5 μM) 756, 0.82×10⁵ ; 802, 0.66×10⁵. ¹ H NMR (C₆ D₆) δ 9.22 (m, 23,26-Ar H), 7.68 (m, 24,25-Ar H), 7.56 (d, 2,17-Ar H), 7.51 (s, 9,10-Ar H), 7.43 (d, 3,16-Ar H), 5.45 (t, 22,27-OR-1 CH₂), 4.94 (m, 1,18-OR-1 CH₂ ; 4,15-OR-1 CH₂), 4.70 (t, 8,11-OR-1 CH₂), 2.30 (m, 22,27-OR-2 CH₂), 2.21 (m, 1,18-OR-2 CH₂ ; 4,15-OR-2 CH₂ ; 8,11-OR-2 CH₂), 1.78 (m, 22,27-OR-3 CH₂), 1.75 (m, 1,18-OR-3 CH₂ ; 4,15-OR-3 CH₂ ; 8,11-OR-3 CH₂), 1.18 (t, 22,27-OR CH₃), 1.13 (m, 1,18-OR CH₃ ; 4,15-OR CH₃), 0.93 (t, 8,11-OR CH₃), 0.63 (s, NH). ¹³ C NMR (C₆ D₆): δ 152.62 (21,28-Ar C), 152.41 (1,18-Ar C; 4,15-Ar C; 5,14-Ar C; 7,12-Ar C; 8,11-Ar C; 19,30-Ar C), 150.73 (22,27-Ar C) 132.02 (22a,26a-Ar C), 129.84 (7a,lla-Ar C), 127.35 (24,25-Ar C), 126.04 (21a,27a-Ar C), 125.30 (4a,14a-Ar C; 18a,30a-Ar C), 125.05 (23,26-Ar C), 120.36 (2,17-Ar C), 120.05 (3,16-Ar C), 118.05 (9,10-Ar C), 77.50 (22,27-OR-1 C), 73.00 (1,18-OR-1 C; 4,15-OR-1 C), 72.22 (8,11-OR-1 C), 33.63 (22,27-OR-2 C), 32.57 (1,18-OR-2 C), 32.47 (4,15-OR-2 C), 32.35 (8,11-OR-2 C), 20.07 (1,18-OR-3 C; 22,27-OR-3 C), 19.99 (4,15-OR-3 C; 8,11-OR-3 C), 14.39 (1,18-OR-4 C; 4,15-OR-4 C; 8,11-OR-4 C; 22,27-OR-4 C). MS-HRFAB exact mass, m/z calcd for C₆₈ H₈₄ N₈ O₈ (M+H)⁺, 1141.6490; found, 1141.6453, 1141.6449. The H₂ N₁ P₃ (OBu) a dark-green solid, is soluble in toluene, CH₂ Cl₂, pyridine and slightly soluble in hexane.

Example 21 H₂ N₀ P₄ (OBu)₈

H₂ N₀ P₄ (OBu)₈, also designated (H₂ PC(OBu)₈) was isolated from the H₂ N_(4-x) P_(x) (OBu)₈ mixture of Example 16 by continuing the chromatography with ethyl acetate. The fraction separated provided 30 mg of H₂ N₀ P₄ (OBu)₈, which represents 5% of weight of H₂ N_(4-x) P_(x) (OBU)₈. UV-vis (λ_(max) nm), ε (M⁻¹ cm⁻¹)) (toluene, 2.1 μM) 739, 0.95×10⁵, 761, 1.1×10⁵. ¹ H NMR (C₆ D₆): δ 7.53 (s, Ar H), 4.91 (t, OR-1 CH₂), 2.20 (m, OR-2 CH₂), 1.72 (m, OR-3 CH₂), 1.04 (t, OR CH₃), -0.28 (s, NH). ¹³ C NMR (C₆ D₆): δ 152.63 (5,7,12,14,19,21,26,28-Ar C), 149.20 (1,4,8,11,15,18,22,25-Ar C), 127.75 (4a,7a,11a,14a,18a,21a,25a,28a-Ar C), 120.33 (2,3,9,10,16,17,23,24-Ar C), 73.01 (OR-1 C), 32.51 (OR-2 C), 19.98 (OR-3 C), 14.37 (OR-4 C). The H₂ N₀ P₄ (OBu)₈, a green solid, is soluble in toluene, CH₂ Cl₂, pyridine and slightly soluble in hexane.

The amounts of the various compounds in the mixture the H₂ N_(4-x) P_(x) (OBu)₈ obtained are not those predicted statistically on the assumption that the two nitriles contribute to ring formation equally; the results are shown in Table I.

                  TABLE I     ______________________________________     Amounts of Components in H.sub.2 N.sub.4-x P.sub.x  (OBu).sub.8  Mixture     (%)     H.sub.2 N.sub.4 P.sub.0                H.sub.2 N.sub.3 P.sub.1                        c-H.sub.2 N.sub.2 P.sub.2                                 t-H.sub.2 N.sub.2 P.sub.2                                        H.sub.2 N.sub.1 P.sub.3                                              H.sub.2 N.sub.0 P.sub.4     ______________________________________     statistical            5       18      27     27     18    5     actual 2       15      24     5      41    12     difference            -3      -3      -3     -22    +23   +7     ______________________________________

The solubility of the octabutoxy compounds of the Examples was determined in hexane, toluene, CHCl₃, pyridine and CH₂ Cl₂ and are presented in Table II.

                  TABLE II     ______________________________________     Solubility                        hex-   tolu-     Ex  Compound       ane    ene  CHCl.sub.3                                          pyridine                                                CH.sub.2 Cl.sub.2     ______________________________________      1  c-SiN.sub.2 P.sub.2 (OBu).sub.8 (OH).sub.2                        ss     s    s     s     s      2  SiN.sub.4 P0(OBu).sub.8 (OH).sub.2                        ss     s    s     s     s      3  SiN.sub.3 P.sub.1 (OBu).sub.8 (OH).sub.2                        ss     s    s     s     s      4  t-SiN.sub.2 P.sub.2 (OBu).sub.8 (OH).sub.2                        ss     s    s     s     s      5  SiN.sub.1 P.sub.3 (OBu).sub.8 (OH).sub.2                        ss     s    s     s     s      6  SiN.sub.0 P.sub.4 (OBu).sub.8 (OH).sub.2                        ss     s    s     s     s      8  c-SiN.sub.2 P.sub.2 (OBu).sub.8                        vs     vs   vs    vs    vs         (OSi(n-C.sub.6 H.sub.13).sub.3).sub.2      9  SiN.sub.4 P.sub.0 (OBu).sub.8 (OSi(n-                        vs     vs   vs    vs    vs         C.sub.6 H.sub.13).sub.3).sub.2     10  SiN.sub.3 P.sub.1 (OBu).sub.8 (OSi(n-                        vs     vs   vs    vs    vs         C.sub.6 H.sub.13).sub.3).sub.2     11  t-             vs     vs   vs    vs    vs         SiN.sub.2 P.sub.2 (OBu).sub.8 (OSi(n-         C.sub.6 H.sub.13).sub.3).sub.2     12  SiN.sub.1 P.sub.3 (OBu).sub.8 (OSi(n-                        vs     vs   vs    vs    vs         C.sub.6 H.sub.13).sub.3).sub.2     13  SiN.sub.0 P.sub.4 (OBu).sub.8 (OSi(n-                        vs     vs   vs    vs    vs         C.sub.6 H.sub.13).sub.3).sub.2     14  SiPc(dib).sub.4 (OBu).sub.8                        I      s    s         (OH).sub.2     16  H.sub.2 N.sub.4 P.sub.0 (OBu).sub.8                        ss     s    s     s     s     17  H.sub.2 N.sub.3 P.sub.1 (OBu).sub.8                        ss     s    s     s     s     18  c-H.sub.2 N.sub.2 P.sub.2 (OBu).sub.8                        ss     s    s     s     s     19  t-H.sub.2 N.sub.2 P.sub.2 (OBu).sub.8                        ss     s    s     s     s     20  H.sub.2 N.sub.1 P.sub.3 (OBu).sub.8                        ss     s    s     s     s     21  H.sub.2 N.sub.0 P.sub.4 (OBu).sub.8                        ss     s    s     s     s     ______________________________________      a ss, slightly soluble (<1 mg/mL);      s, soluble (˜1-5 mg/mL);      vs, very soluble (>5 mg/mL).

The solubilities of the solid phthalocyanine complexes in organic solvents as shown in Table II indicate that for comparable pairs of complexes, the complex with the larger axial groups is more soluble.

All of the phthalocyanine complexes of the above examples display intense colors. SiPc(OBu)₈ (OSi (n--C₆ H₁₃)₃)₂ has, for example, a particularly beautiful green color in solution.

Ultraviolet-Visible Light Absorption Analysis

The twenty-eight maxima of the Q-bands of eighteen of the compounds made, Table III can be grouped into three sets. The first contains 10 maxima in a 24 nm range running from 739-763 nm. The second contains 9 maxima in a 32 nm range running from 793-825 nm, and the third 9 maxima in a 14 nm range running from 851-865 nm, as shown in Table III.

                                      TABLE III     __________________________________________________________________________     Q-Band Maxima     range    band     limits           span              position                   ε    compound     (nm)  (nm)              (nm) (M.sup.-1 cm.sup.-1 /10.sup.5)                          type.sup.a                             Δ.sup.b                                ring core                                        ligands     __________________________________________________________________________     1 739-           24 739  0.95   d     N.sub.0 P.sub.4                                     H       763              747  2.3    s  8  N.sub.0 P.sub.4                                     Si OSiR.sub.3              749         s  2  N.sub.0 P.sub.4                                     Si OH              750  0.98   d  1  t-N.sub.2 P.sub.2                                     H              756  0.82   d  6  N.sub.1 P.sub.3                                     H              760  1.5    d  4  t-N.sub.2 P.sub.2                                     Si OSiR.sub.3              761  2.2    d  1  N.sub.1 P.sub.3                                     Si OSiR.sub.3                   1.1    d  1  N.sub.0 P.sub.4                                     H              762         d  1  N.sub.1 P.sub.3                                     Si OH              763         d  1  t-N.sub.2 P.sub.2                                     Si OH     2 793-           32 793         d  30 N.sub.1 P.sub.3                                     Si OH       825              794  1.5    d  1  N.sub.1 P.sub.3                                     Si OSiR.sub.3              802  0.66   d  8  N.sub.1 P.sub.3                                     H              804  1.9    s  2  c-N.sub.2 P.sub.2                                     Si OSiR.sub.3              805         s  1  c-N.sub.2 P.sub.2                                     Si OH              807  1.9    s  2  c-N.sub.2 P.sub.2                                     H              814  0.99   d  7  N.sub.3 P.sub.1                                     H              820  1.6    d  6  N.sub.3 P.sub.1                                     Si OSiR.sub.3              825         d  5  N.sub.3 P.sub.1                                     Si OH     3 851-           14 851  1.2    d  26 t-N.sub.2 P.sub.2                                     Si OSiR.sub.3       865                   0.89   d  0  N.sub.3 P.sub.1                                     H              852  0.75   d  1  t-N.sub.2 P.sub.2                                     H              857  1.3    d  5  N.sub.3 P.sub.1                                     Si OSiR.sub.3              859         d  2  t-N.sub.2 P.sub.2                                     Si OH              861         d  2  N.sub.3 P.sub.1                                     Si OH              862  2.0    s  1  N.sub.4 P.sub.0                                     H              864  2.0    s  2  N.sub.4 P.sub.0                                     Si OSiR.sub.3              865         s  1  N.sub.4 P.sub.0                                     Si OH     __________________________________________________________________________      .sup.a s, from single maximum band; d, from double maximum band.      .sup.b nm from preceding maximum

The bands of the second set have maxima that are near or in the range which is most common for the line of the ordinary GaAlAs diode laser, 800-810 nm; such lasers are used for photodynamic therapy. Of the bands within this set, the 804, 805 and 807 nm bands are of particular interest because they are sharp, very intense and have maxima in the part of the diode laser band range which is most common. Since the 804, 805 and 807 nm bands belong to c-H₂ N₂ P₂ (OBu)₈ c-SiN₂ P₂ (OBu)₈ (OH)₂ and c-SiN₂ P₂ (OBu) (OSi (n--C₆ H₁₃)₃)₂₁ these compounds become the ones of particular interest. These compounds have the further advantage of being stable, and highly soluble in common organic solvents, for example, toluene.

In addition, phthalocyanines and naphthalocyanines that have Q-band maxima anywhere between about 650 and 1000 nm are made by attaching suitable substituents to them and placing suitable elements in their centers. For example, large displacements of the maxima of phthalocyanines can be obtained by placing alkoxy groups on their 1,4 positions or by fusing benzo rings at their 2,3 positions. Small or tuning displacements can be obtained by placing various groups at their 2,3-positions.

Although certain embodiments of this invention have been shown and described, various adaptations and modifications can be made without departing from the scope of the invention as defined in the appended claims. 

It is claimed:
 1. A method for making silicon phthalocyanines and naphthalocyanines comprising the following steps:a. providing a metal-free phthalocyanine or naphthalocyanine; b. reacting the metal-free phthalocyanine or naphthalocyanine with HSiCl₃ to provide a first reaction product; c. then reacting the reaction product of step b with water to provide a second reaction product; and d. extracting the silicon phthalocyanine or naphthalocyanine from the second reaction product.
 2. The method of claim 1, wherein the metal-free phthalocyanine or naphthalocyanine is reacted with the HSiCl₃ in the presence of an amine and an organic solvent.
 3. The method of claim 2, wherein the solvent is CH₂ Cl₂.
 4. The method of claim 1 wherein the extraction of step d employs a volatile solvent.
 5. A phthalocyanine compound having the following structure: ##STR6## wherein: R is Si(OSiR'₃)₂, where R' is an alkyl group having from 1-18 carbon atoms;R¹ and R² are both H, or are joined to form a benzene ring; R³ and R⁴ are both H, or are joined to form a benzene ring; R⁵ and R⁶ are both H, or are joined to form a benzene ring; R⁷ and R⁸ are both H, or are joined to form a benzene ring; and R" is an alkyl group having from 1 to 18 carbon atoms.
 6. The phthalocyanine compound of claim 5, wherein R is Si(OSi(n-C₆ H₁₃)₃)₂ and where R1, R2, R3, R4, R5, R6, R7 and R8 are all H.
 7. The phthalocyanine compound of claim 5, wherein R is Si(OSi(n-C₆ H₁₃)₃)₂ and where R1 and R2 are joined to form a benzene ring, and R3, R4, R5, R6, R7 and R8 are all H.
 8. The phthalocyanine compound of claim 5, wherein R is Si(OSi(n-C₆ H₁₃)₃)₂ and where R1 and R2 are joined to form a benzene ring; R3 and R4 are joined to form a benzene ring, and R5, R6, R7 and R8 are all H.
 9. The phthalocyanine compound of claim 5, wherein R is Si(OSi(n-C₆ H₁₃)₃)₂, and where R1 and R2 are joined to form a benzene ring; R5 and R6 are joined to form a benzene ring, and R3, R4, R7 and R8 are all H.
 10. The phthalocyanine compound of claim 5, wherein R is Si (OSi (n--C₆ H₁₃)₃)₂, and where R1 and R2 are joined to form a benzene ring; R3 and R4 are joined to form a benzene ring; R5 and R6 are joined to form a benzene ring; and R7 and R8 are both H.
 11. The phthalocyanine compound of claim 5, wherein R is Si(OSi(n--C₆ H₁₃)₃)₂, and where R1 and R2 are joined to form a benzene ring; R3 and R4 are joined to form a benzene ring; R5 and R6 are joined to form a benzene ring; and R7 and R8 are joined to form a benzene ring.
 12. The phthalocyanine compound of claim 5, wherein R is Si(OH)₂, and where R1, R2, R3, R4, R5, R6, R7 and R8 are all H.
 13. The phthalocyanine compound of claim 5, wherein R is Si(OH)₂, and where R1 and R2 are joined to form a benzene ring, and R3, R4, R5, R6, R7 and R8 are all H.
 14. The phthalocyanine compound of claim 5, wherein R is Si(OH)₂ and where R1 and R2 are joined to form a benzene ring; R3 and R4 are joined to form a benzene ring, and R5, R6, R7 and R8 are all H.
 15. The phthalocyanine compound of claim 5, wherein R is Si(OH)₂ and where R1 and R2 are joined to form a benzene ring; R5 and R6 are joined to form a benzene ring, and R3, R4, R7 and R8 are all H.
 16. The phthalocyanine compound of claim 5, wherein R is Si(OH)₂, and where R1 and R2 are joined to form a benzene ring; R3 and R4 are joined to form a benzene ring; R5 and R6 are joined to form a benzene ring; and R7 and R8 are both H.
 17. The phthalocyanine compound of claim 5, wherein R is Si(OH)₂ and where R1 and R2 are joined to form a benzene ring; R3 and R4 are joined to form a benzene ring; R5 and R6 are joined to form a benzene ring; and R7 and R8 are joined to form a benzene ring.
 18. A phthalocyanine compound having the following structure: ##STR7## wherein: two N, selected from the group of N1, N2, N3, and N4, have a H bound to or associated therewith;and the structure contains from one to three benzene rings selected form the following:a benzene ring formed by the joining of R¹ and R² ; a benzene ring formed by the joining of R³ and R⁴ ; a benzene ring formed by the joining of R⁵ and R⁶ ; a benzene ring formed by the joining of R⁷ and R⁸.
 19. The phthalocyanine compound of claim 18, wherein R1 and R2 are joined to form a benzene ring, and R3, R4, R5, R6, R7 and R8 are all H.
 20. The phthalocyanine compound of claim 18, wherein R1 and R2 are joined to form a benzene ring; R3 and R4 are joined to form a benzene ring, and R5, R6, R7 and R8 are all H.
 21. The phthalocyanine compound of claim 18, wherein R1 and R2 are joined to form a benzene ring; R5 and R6 are joined to form a benzene ring, and R3, R4, R7 and R8 are all H.
 22. The phthalocyanine compound of claim 18, wherein R1 and R2 are joined to form a benzene ring; R3 and R4 are joined to form a benzene ring; R5 and R6 are joined to form a benzene ring; and R7 and R8 are both H.
 23. A phthalocyanine compound having the following structure: ##STR8## wherein: R is Si(OH)₂ ;R' and R² are both H, or are joined to form a benzene ring; R³ and R⁴ are both H, or are joined to form a benzene ring; R⁵ and R⁶ are both H, or are joined to form a benzene ring; R⁷ and R⁸ are both H, or are joined to form a benzene ring; and R" is an alkyl group having from 1 to 18 carbon atoms.
 24. The phthalocyanine compound of claim 22, wherein R1 and R2 are joined to form a benzene ring, and R3, R4, R5, R6, R7 and R8 are all H.
 25. The phthalocyanine compound of claim 22, wherein R1 and R2 are joined to form a benzene ring; R3 and R4 are joined to form a benzene ring, and R5, R6, R7 and R8 are all H.
 26. The phthalocyanine compound of claim 22, wherein R1 and R2 are joined to form a benzene ring; R5 and R6 are joined to form a benzene ring, and R3, R4, R7 and R8 are all H.
 27. The phthalocyanine compound of claim 22, wherein R1 and R2 are joined to form a benzene ring; R3 and R4 are joined to form a benzene ring; R5 and R6 are joined to form a benzene ring; and R7 and R8 are both H. 